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Exam #3
c) (4) Does this model for the gas obey the third law of thermodynamics? Explain
the reasoning behind your answer.
Which of the following graphs could represent the behavior of the total entropy change
∆S (solid plus bath) as a function of the temperature difference TB − Ti ? Explain
your choice.
I II III IV V
Astronomers have discovered that there exist in the interstellar medium clouds of
“dust grains” whose chemical composition may include silicates (like sand) or carbon-
containing compounds (like graphite or silicon carbide). Evidence indicates that many
of these grains have a needle like shape.
If the rotational motion of a dust grain is to be described in terms of its principal axes
(1,2, and 3) the appropriate coordinates (angles) and canonically conjugate angular
momenta are θ1 , θ2 , θ3 and L1 , L2 , L3 . In terms of these variables the classical
Hamiltonian for a single grain is given by
1 2 1 2 1 2
H= L1 + L2 + L
2I1 2I2 2I3 3
where Ii is the moment of inertia about the ith principal axis. Assume that a dust
cloud is in thermal equilibrium at a temperature T .
a) (10) Find an analytic expression (no unevaluated integrals) for the joint prob-
ability density function for the canonical variables, p(θ1 , θ2 , θ3 , L1 , L2 , L3 ), for a
single dust grain.
b) (7) Assume that axis 3 is parallel to the long axis of the grain and that I3 <<
I1 = I2 . Will the angular momentum of a dust grain be more likely to be
parallel or perpendicular to the long (3) axis? Find a quantitative result to
support your contention.
c) (7) Find the rotational contribution of the grains to the entropy of a dust cloud
containing N dust grains.
d) (3) Does this model for the rotational motion of the dust grains obey the third
law of thermodynamics? Explain the reasoning behind your answer.
e) (3) Should this model of rotational motion exhibit energy gap behavior? Why?
If a perfect crystal is cleaved along a symmetry direction, the resulting surface could
expose a single geometrically flat plane of atoms. Alternatively, if the crystal is cut at
a slight angle with respect to this direction, the resulting surface might take the form
of a series of terraces of fixed width separated by steps of height corresponding to
one atomic layer. This situation is illustrated in figure 1. The steps themselves may
not be straight lines, but may have kinks when viewed from above as shown in figure
2. If impurity atoms were adsorbed on such a surface, their energy could depend on
where they reside relative to the steps.
Consider N identical xenon atoms adsorbed on a silicon surface which has a total of
M possible adsorption sites. There are three different types of site that the xenon
could occupy. They would prefer to snuggle into a corner site at a kink in a step. One
percent of the sites are corner sites, and their energy defines the zero of the energy
scale for adsorbed atoms. Next in preference are edge sites. Fourteen percent of the
M sites are edge sites with an energy ∆ above that of a corner site. The majority
(85%) of the adsorption sites are face sites, but they have an energy which is 1.5∆
above that of the corner sites. M is so large compared to N competition for a given
site can be neglected; the xenon atoms can be considered completely independent.
You may neglect the kinetic energy of the adsorbed atoms.
a) (7) Find the partition function, Z(N, T ), for the xenon atoms in terms of the
parameters M and ∆.
b) (4) Find the ratio of xenon atoms on face sites to the number on corner sites.
c) (10) Find an expression for the heat capacity of the adsorbed xenon atoms in
the limit kT ∆.
d) (3) What is the probability that a given xenon atom will be found on a face site
in the limit kT ∆?
e) (3) What is the limit of the entropy of this system as T → ∞ ?
f) (3) Should this model for adsorbed atoms exhibit energy gap behavior? Why?
∂x
z Surface S A SdA
∂x ∂y ∂z
= −1
∂y z ∂z x ∂x y
Reversible E Z E dZ
cell
INTEGRALS
Dielectric E P EdP
material
∞
xn −x/a
e dx = n! an
0 a
Magnetic H M HdM
∞
material
x2n
e−x /2σ = 1 · 3 · 5 · · · (2n − 1)σ 2n
2 2
√
2πσ 2
−∞
1
eax dx = e ax THERMODYNAMIC POTENTIALS
a
For a system in which the increment of work done
on the system is dW = Xdx
STERLING’S APPROXIMATION
Energy E dE=TdS+Xdx
Helmholtz free energy F=E-TS dF=-SdT+Xdx
ln K! ≈ K ln K − K when K >> 1
Gibbs free energy G=E-TS-Xx dG = -SdT-xdX
Enthalpy H=E-Xx dH=TdS-xdX
dΩ = sin θ dθ dφ
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